Photolysis of a High‐Spin Azidoiron(III) Complex Studied by Time‐Resolved Fourier‐Transform Infrared Spectroscopy

The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the meta...

Full description

Saved in:
Bibliographic Details
Published in:Chemistry : a European journal 2017-05, Vol.23 (28), p.6746-6751
Main Authors: Torres‐Alacan, Joel, Vöhringer, Peter
Format: Article
Language:English
Subjects:
Acetonitrile
Anions
Carbon monoxide
Carbonyl compounds
Carbonyls
Chemistry
Excitation spectra
Flash photolysis
Fourier transforms
high-valent iron
Infrared lasers
Infrared spectroscopy
Iodides
photochemistry
Photolysis
Photoreduction
Quenching
Room temperature
Scavenging
Spectrum analysis
time-resolved
transition-metal complexes
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The laser‐flash photolysis of the high‐spin azidoiron(III) complex [FeIII(Me3Cyclam‐ac)(N3)]PF6 ([1]PF6) in liquid acetonitrile solution at room temperature was explored by time‐resolved Fourier‐transform infrared spectroscopy. Excitation of [1] at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ ([2]) and azidyl radicals. Both photoproducts were detected independently through scavenging experiments. The metal‐containing fragment was quenched with carbon monoxide to generate an iron(II) carbonyl complex, whereas the nitrogen‐containing fragment was quenched with iodide to form azide anions. In the presence of N3−, the photoreduction created the elusive hexanitrogen radical anion N6.− as a transient byproduct. A closer look at photolysis: Time‐resolved infrared spectroscopy is used to explore the liquid‐phase photochemistry of the high‐spin ferric azide complex [FeIII(Me3Cyclam‐ac)(N3)]PF6. Excitation of the complex at 480 and 266 nm induced a photoreduction of the metal center and generated [FeII(Me3Cyclam‐ac)(NCCH3)]+ and azidyl radicals.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201700960